Supporting Infromation. Helical Lanthanide(III) Complexes with Chiral Nonaaza Macrocycle.

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1 Supporting Infromation Helical Lanthanide(III) Complexes with Chiral Nonaaza Macrocycle. Janusz Gregoliński, Przemysław Starynowicz, KimNgan T. Hua, Jamie L. Lunkley, Gilles Muller * and Jerzy Lisowski* Fig. S1. ESI MS spectra of 10-6 M methanol solutions of the (M)-[CeL RRRRRR ](NO 3 ) 3 2H 2 O, (M)- [PrL RRRRRR ](NO 3 ) 3 H 2 O, [NdL RRRRRR ](NO 3 ) 3 0.5H 2 O and (M)-[GdL RRRRRR ](NO 3 ) 3 4H 2 O complexes. S1

2 Fig. S2. ESI MS spectra of 10-6 M methanol solutions of the (M)-[ErL RRRRRR ](NO 3 ) 3 ] CHCl 3 2.5H 2 O, (P)- [ErL RRRRRR ](NO 3 ) 3 7H 2 O, (M)-[LuL RRRRRR ](NO 3 ) 3 CHCl 3 2H 2 O and (P)-[LuL RRRRRR ](NO 3 ) 3 7H 2 O complexes. S2

3 Fig. S3. Views of the structure of the (M)-[PrLRRRRRR]3+ (left), (P)-[CeLSSSSSS]3+ (middle) and (P)-[LuLRRRRRR]3+ cations along (upper pictures) and perpendicular to the C2 axis (lower pictures). S3

4 Description of X-ray crystal structures The crystals of (M)-[PrL RRRRRR ](NO 3 ) 3 3CH 3 CN 3 2 / 3 H 2 O, (P)- [CeL SSSSSS ](NO 3 ) 3 4CH 3 CN 3H 2 O and (P)-[LuL RRRRRR ](NO 3 ) / 8 CH 3 CN 3 3 / 4 H 2 O are composed of the complex cation [LnL] 3+, uncoordinated nitrate anions, and partially disordered solvent molecules (Supporting Table S1). In each complex the cation is surrounded by all nine nitrogen atoms of the ligand and is not coordinated by the solvent molecules or counteranions The Type I and Type II diastereomers differ in the configuration at the amine nitrogen atoms. In Type I complexes, the helical twist of the macrocycle imposes the S, S chirality 18 of the nitrogen atoms of the unique cyclohexane ring and R, S chirality of the nitrogen atoms of the two equivalent cyclohexane rings. In Type II complexes, the opposite helix direction imposes also different chirality at the donor nitrogen atoms; the nitrogen atoms of the unique cyclohexane ring positioned on the symmetry axis are of R configuration, while the remaining four amine nitrogen atoms are of S configuration. The three 2,6-substituted pyridine fragments of the macrocycle L in the (P)- [LuL RRRRRR ] 3+ complex form propeller-like structure (Fig. S4), similar to that observed in tris(dipicolinato)lanthanide anions 19 or some pyridine-containing triple-helical 8 lanthanide(iii) complexes. Similarly to the tris(dipicolinato)lanthanide anions, the coordination figure of the metal cation may be viewed as a distorted tricapped trigonal prism (TCTP) with twisted bases, where the amine atoms N2, N3, N6 and N5, N8, N9 span the bases, and the pyridine atoms N1, N4, N7 form the caps. The further distortion of the coordination sphere results from the fact that the D 3 symmetry is not observed and only one two-fold symmetry axis of the parent idealized tricapped trigonal prism structure is retained. Similar propeller-like arrangement of pyridine fragments is also observed for the (P)-[CeL SSSSSS ] 3+ and (M)- S4

5 [PrL RRRRRR ] 3+ cations (Fig. S5), but the deviations from the D 3 symmetry and tricapped trigonal prism structure are even greater. Fig. S4. The propeller-like arrangement of the pyridine fragments in the (P)-[LuL RRRRRR ] 3+ complex (cyclohexane rings of the L RRRRRR macrocycle are not shown for clarity) Fig. S5. The propeller-like arrangement of the pyridine fragments in the (M)-[PrL RRRRRR ] 3+ complex (cyclohexane rings of the L RRRRRR macrocycle are not shown for clarity) S5

6 Additionally, the crystals of the approximate composition (M)- [CeL RRRRRR ][Ce(NO 3 ) x (H 2 O) y ](NO 3 ) (6-x) solv. (orthorhombic C222 1, a = (1), b = (1), c = (2)) were obtained by slow diffusion of diethyl ether into the CH 3 OH/CH 3 CN solution of the (M)-[CeL RRRRRR ](NO 3 ) 3 2H 2 O complex, whereas the crystals of the approximate composition (M)-[PrL RRRRRR ][Pr(NO 3 ) x (H 2 O) n ](NO 3 ) (5-x) Cl solv. (orthorhombic C222 1, a = (4), b = (5), c = 33.79(10)) were obtained by the slow evaporation of the solution containing the (M)-[PrL RRRRRR ](NO 3 ) 3 H 2 O complex in chloroform/methanol mixture. Although the solvent and counteranion molecules were severely disordered and crystals were too small to obtain satisfactory solved molecular structures, the model structures obtained definitely show the M-helical conformation of the ligand in both complexes (Fig. S6). For similar reasons, the structure of the crystals of the composition (P)-[YbL RRRRRR ][Yb 0.5 (NO 3 ) 1.5 (H 2 O) 1.5 ](NO 3 ) H 2 O (trigonal P322 1, a=15.486(2), c = (8)), obtained after one month from the methanol/acetonitrile solution of the (M)-[YbL RRRRRR ] 2 [Yb(NO 3 ) 5 ](NO 3 ) 4 4H 2 O complex, was not satisfactorily solved. However, the model structure clearly showed the (P)-helical conformation of the conversion product of the starting (M)-helical complex (Fig. S7). S6

7 Fig. S6. The model structures of the cationic complexes: (M)-[CeL RRRRRR ] 3+ (left) and (M)-[PrL RRRRRR ] 3+ (right) in highly disordered (M)-[CeL RRRRRR ][Ce(NO 3 ) x (H 2 O) y ](NO 3 ) (6-x) solv. and (M)- [LnL RRRRRR ][Ln(NO 3 ) x (H 2 O) n ](NO 3 ) (5-x) Cl solv. crystals. Fig. S7. Model structure of (P)-[YbL RRRRRR ][Yb 0.5 (NO 3 ) 1.5 (H 2 O) 1.5 ](NO 3 ) H 2 O. S7

8 Fig. S8. The CD spectra of the two enantiomeric [PrL](NO 3 ) 3 H 2 O complexes in H 2 O solutions ( M): (M)-[PrL RRRRRR ] 3+ (green )/ (P)-[PrL SSSSSS ] 3+ (blue). Fig. S9. The CD spectra of the two diastereomers of the Lu(III) complexes with L RRRRRR in H 2 O solutions ( M): (M)-[LuL RRRRRR ] 3+ (green) / (P)-[LuL RRRRRR ] 3+ (blue). The spectra were recorded at RT during 20 minutes after both complexes had been dissolved. The solution of the (M)-[LnL RRRRRR ] 3+ isomer includes ca 5% of free ligand L RRRRRR (based on 1 H NMR spectrum carried out during the same time). S8

9 Fig. S10. 1 H NMR spectra of (M)-[EuL RRRRRR ](NO 3 ) 3 4H 2 O in CD 3 OD solution ( M) immediately after being dissolved (upper trace) and after 3 days (lower trace). (* - residual solvent signals) S9

10 Fig. S11. The dependence of the relative concentration of the (M)- and (P)-diastereomers on the heating time of the M solution of (M)-[LnL RRRRRR ](NO 3 ) 3 ] (D 2 O, 318 K). The red, blue and black plots represent the (M)-, (P)- [LnL RRRRRR ] 3+ complexes, and the free ligand L RRRRRR, respectively. S10

11 Fig. S12. 1 H NMR spectra of (P)-[YbL RRRRRR ](NO 3 ) 3 6H2O ( M) in D 2 O solution (1), in D 2 O solution in the presence of 3 equivalents of NaOH (2), in 20% DCl solution measured after 17 days (3). (S solvent signal) S11

12 Fig. S13. The 1 H NMR spectrum of the mixture of Eu(III) complexes enriched in the (P)-diastereomer with a (M)- [EuL RRRRRR ] 3+ /(P)-[EuL RRRRRR ] 3+ ratio equal to 1:1 (the M D 2 O solution, 298 K) Fig S14. Upper trace -the 1 H NMR spectrum of the mixture of Eu(III) complexes enriched in the (P)-diastereomer with a (M)-[EuL RRRRRR ] 3+ /(P)-[EuL RRRRRR ] 3+ ratio equal to 2:1. Lower trace the 1 H NMR of the same sample measured after 20 days. ( M D 2 O solution, 298 K) S12

13 Supporting Fig S15. The 1 H NMR spectrum of the (M)-[PrL RRRRRR ](NO 3 ) 3 H 2 O complex in CD 3 CN/CD 3 OD 8:1 v/v solution (298K). See Scheme 1 for the labeling of the positions. S13

14 Fig. S16. The 1 H NMR spectrum of the (M)-[CeL RRRRRR ](NO 3 ) 3 2H 2 O complex in D 2 O solution ( M, 298 K) Fig. S17. 1 H NMR spectrum of the(m)-[ndl SSSSSS ](NO 3 ) 3 0.5H 2 O complex in D 2 O solution ( M, 298 K). S14

15 Fig S18. 1 H NMR spectra of the (M)-[TbL RRRRRR ](NO 3 ) 3 4H 2 O complex (black trace) and of the sample enriched in the (P)-isomer with a (M)-[TbL RRRRRR ] 3+ /(P)-[TbL RRRRRR ] 3+ ratio equals to 10:8 in D 2 O solutions ( M, 298 K). Fig. S19. 1 H NMR spectra of the (M)-[ErL RRRRRR ](NO 3 ) 3 CHCl 3 2.5H 2 O (upper trace) and (P)- [ErL RRRRRR ](NO 3 ) 3 7H 2 O complexes (lower trace) in D 2 O solutions ( M, 298 K). S15

16 Fig. S20. The NMR spectra of (M)-[YbL RRRRRR ](NO 3 ) 3 CHCl 3 H 2 O complex in CD 3 OD solution (298 K), illustrating the doubling of the resonances due to isotope effect. The spectra were measured 10 min. (top), 3 hrs (middle) and 22 hrs (bottom) after preparation of the sample. S16

17 Fig. S21. Fragments of the 1 H NMR spectra of the (M)-[LuL RRRRRR ](NO 3 ) 3 CHCl 3 2H 2 O (black trace) and (P)- [LuL RRRRRR ](NO 3 ) 3 7H 2 O (red trace) in D 2 O solutions ( M, 298 K). S17

18 1 H NMR signal assignment Because some of the 2D NMR correlations were difficult to observe due to paramagnetic relaxation in the case of Pr(III) complex and partial signal overlap in the case of Lu(III) complex, only the combined results obtained from COSY, TOCSY, NOESY, ROESY and HMQC spectra allowed unequivocal assignment of all resonances. Fig. S22. The TOCSY spectrum of the (P)-[LuL RRRRRR ](NO 3 ) 3 7H 2 O complex (D 2 O, 298K). The red and green colors indicate the spin systems e+f+g+h+i+j+k+l+m+n+c+d+nh +NH +o+p and v+w+x+y+z+t+u+nh, respectively. See Scheme 1 for the labeling of the positions. S18

19 The TOCSY spectrum of the D 2 O solution of (P)-[LuL RRRRRR ](NO 3 ) 3 complex identifies a group of 16 correlated signals and a group of 8 correlated signals (Fig. S22). These two spin systems correspond to two sets of cyclohexane protons: e+f+g+h+i+j+k+l+m+n and v+w+x+y+z, respectively, together with the adjacent NH and methylene bridge protons: c+d+nh +NH +o+p and t+u+nh, respectively (see Scheme 1 for labelling). The HMQC spectrum identifies the 1 H NMR signals of pairs of geminal protons and confirms the assignment of the group of the 3 signals of the exchangeable NH protons (Supporting Fig. S23). This spectrum also allows finding the signals of cyclohexane CHNH protons that do not have a geminal partner, i.e. signal v from the above group of eight TOCSY-correlate signals and the pair of signals e+n from the above group of sixteen TOCSY-correlate signals. The identification of the e+n pair is additionally confirmed by observation of the COSY correlation (Supporting Fig. S24) between these two signals. The assignment of signals starts with the easily assigned signal of pyridine proton a (Scheme 1), positioned on the symmetry axis, that integrates to 1H, while all other signals integrate to 2H. Signal a is ROESY (Fig. 5), NOESY and COSY (Supporting Fig. S24) correlated to a signal of aromatic proton b. The signal of the proton b is in turn ROESY correlated to the signals of the pair of geminal protons c and d, and signal of proton e. Signals of protons e and c are also ROESY correlated. The assignment of signal e allows for finding of the signal of the proton n, since the pair e+n has been already identified. Signal of proton n is ROESY correlated to the signals of the pair of geminal protons o and p, and ROESY and COSY correlated to the signal of amine proton NH. Similarly, the signals of methylene bridge protons c and d are COSY correlated to signal of amine proton NH (overlapped with signal of proton n). Thus the remaining COSY correlated signals of methylene bridge and amine proton correspond to positions t, u and NH, respectively. The signals of geminal protons o and p are ROESY correlated to signal of aromatic proton q, similarly the signals of geminal protons t and u are ROESY correlated to the signal of aromatic proton s. The analysis of the remaining COSY and NOESY/ROESY correlations within the cyclohexane rings S19

20 allows assignment of the remaining signals (Supporting Fig. S25). The HMQC spectrum in combination with the assignment of 1 H NMR signals enables also the assignment of 13 C NMR signals of the corresponding carbon atoms (Supporting Fig. S23). Similar analysis was also performed for the 2D NMR spectra of the DMSO-d6 solution of the Lu(III) complex and the CD 3 CN/CD 3 OD solution of the Pr complex (Fig. S15). Fig. S23. HMQC spectrum of the (P)-[LuL RRRRRR ](NO 3 ) 3 7H 2 O complex in D 2 O solution ( M, 298 K) S20

21 Fig. S24. COSY spectrum of the (P)-[LuL RRRRRR ](NO 3 ) 3 7H 2 O complex in D 2 O solution ( M, 298 K) S21

22 Fig. S25. The assignment of the signals in the 1 H NMR spectrum of the (P)-[LuL RRRRRR ](NO 3 ) 3 7H 2 O complex in D 2 O solution ( M, 298 K) S22

23 Fig. S26. The expanded region of Fig. S20; the 1 H NMR spectra of the (M)-[YbL RRRRRR](NO 3 ) 3 ] CHCl 3 H 2 O complex in CD 3 OD solution (298 K), illustrating the doubling of the resonances due to isotope effect. The spectra were measured after 10 min (top), 1 hr, 3 hrs, 8 hrs and 22 hrs after preparation of the sample. The small signals in the bottom spectrum are due to the (P)-diastereomer formed in the helicity inversion process. S23

24 Supporting Fig. S27. The fragments of the 1 H NMR spectra (298K, CD 3 OD) of (M)- [PrL RRRRRR ](NO 3 ) 3 H 2 O complex, illustrating the disappearing of NH signal and the influence of added acid/base. A F : spectra measured after 0.16 h, 0.8 h, 1.8 h, 2.8h, 4.8h and 13h, respectively; G spectrum of a sample containing 10 µl of 6% HNO 3 measured after 4 h; G spectrum of a sample containing 5 µl of N(C 2 H 5 ) 3 measured after 0.66 h. S24

25 Luminescence sensitization determination The luminescence sensitization (η sens ) value was determined for the Eu(III) complex using the following equation 1 : Q Eu tot Eu = ηisc ηet Q = ηsens Q Eu where Q Eu tot is the europium-centred luminescence quantum yield obtained upon ligand excitation (0.03%), Q Eu the intrinsic luminescence quantum yield of the Eu(III) ion, η sens the efficiency of the luminescence sensitization by the ligand, η ISC the efficiency of the intersystem crossing process from the ligand singlet to triplet state, and η ET the efficiency of the ligand-to-metal energy transfer. The intrinsic quantum yield Q Eu is defined as the ratio between the observed and radiative lifetimes of the Eu( 5 D 0 ) level: Q Eu = τ obs/ τ R where the radiative lifetime τ R can be estimated from: τ R = A MD,0 1 n 3 I I MD tot A MD,0 is the spontaneous emission probability of the Eu( 5 D 0 7 F 1 ) transition (14.65 s -1 ), n is the refractive index (1.33 for the MeOH solution) and I MD /I tot is the intensity ratio of the Eu( 5 D 0 7 F 1 ) transition to the total emission of the 5 D 0 level. For the Eu(III) complex with L RRRRRR, I MD /I tot = 0.14, leading to τ R = 4.1 ms, Q Eu = (τ obs = 0.18 ms) and η sens = As a comparison, η sens values of 0.03 (Q Eu L = 1.4%), (Q Eu L = 0.01%), and in the range of (Q Eu L ~1%) have been obtained for Eu(III) 1:1 and 1:2 complexes with the chiral ligand 2,6-bis(1-Sneopentylbenzimidazol-2-yl)pyridine, 2 and for Eu(III) 1:1 complexes with nitrobenzoic acid ligand derivatives, 3 respectively. References S25

26 (1) Wertz, M. H. V.; Jukes, R. T. F.; Verhoeven, J. W. Phys. Chem. 1985, 89, (2) Muller, G.; Maupin, C. L.; Riehl, J. P.; Birkedal, H.; Piguet, C.; Bunzli, J.-C. G. Eur. J. Inorg. Chem., 2003, (3) de Bettencourt-Dias, A; Viswanathan, S. Dalton Trans, 2006, L L Gd Gd Tb Tb Eu Eu E / 10 3 cm -1 ) E / 10 3 cm -1 Figure S28. Left: Time-resolved emission spectra of L RRRRRR and its Ln(III)-containing complexes in frozen MeOH solutions at 77 K and recorded with time delays of 0.1 or 0.5 ms. Right: Emission spectra of L RRRRRR and its Ln(III)-containing complexes in MeOH solutions at 295 K ( M and M, respectively). S26

27 I Intensity (arb. units) Wavenumbers (cm -1 ) Figure S29. Circularly polarized luminescence (upper curve) and total luminescence (lower curve) spectra in the spectral range of the 5 D 4 7 F 5 transition of (M)-[TbL RRRRRR ] 3+ measured before (black) and after (green) this M complex solution in MeOH was heated at 328 K for three weeks, upon excitation at 284 nm, respectively. S27

28 Intensity (arb. unit) Time (min) Time (min) Fig. S30. Time dependence of the time-resolved emission intensities of the Eu(III)-containing complex with L RRRRRR in M CD 3 OD solution at 295 K. The luminescence intensity has been monitored at 615 nm for 200 (left) and 6000 minutes (right). S28

29 Kinetic analysis The k 1 rate of conversion of the (M)-[LnL RRRRRR ] 3+ diasteromer to the (P)-[LnL RRRRRR ] 3+ diastereomer: ( M ) LnL k1 k 2 ( P) LnL was estimated on the basis of the equations: [( M ) LnL] 0 [( M ) LnL] eq [( P) LnL] eq ln k1 = ( k1+ k1) t and K [( M ) LnL] t [( M ) LnL] eq = = eq [( M ) LnL] eq k2 The sum of k 1 and k 2 was obtained from the plots of the negative natural logarithm of the concentration of (M)-diastereomer in time minus the equilibrium concentration of this diastereomer versus time. For the (M)-[LuL RRRRRR ](NO 3 ) 3 CHCl 3 2H 2 O complex the conversion to the (P)- diastereomer is practically complete and the rate constant was based on an approximation of the first-order reaction. The partial decomposition of the complexes to the free ligand was not taken into account in the kinetic analysis. The analysis yielded the rough estimation of k 1 rate constants to be equal to 1x10-6 s -1, 1.4x10-6 s -1, 6.5x10-6 s -1 and 3.1x10-6 s -1 for the Tb, Er, Yb and Lu complexes, respectively. The first-order rates of H/D exchange corresponding to the reaction : was calculated by analyzing the plots of natural logarithm of the intensity of the NH signals vs. time. S29

30 9 8,5 8 y = 6,86E-06x + 4,67E+00 -ln([myb]-[myb]eq) 7,5 7 6,5 6 5,5 5 4, time [s] Fig. S31. The plot of the negative natural logarithm of the concentration of (M)-diastereomer in time minus the equilibrium concentration of this diastereomer versus time for the (M)- [YbL RRRRRR ](NO 3 ) 3 ] CHCl 3 H 2 O complex (D 2 O, 318 K). 0,012 0,01 y = 7,97E-03e -3,15E-06x 0,008 [MLu] 0,006 0,004 0, time [s] Fig. S32. The plot of the concentration of (M)-diastereomer vs. time for the (M)- [LuL RRRRRR ](NO 3 ) 3 CHCl 3 2H 2 O complex (D 2 O, 318 K). S30

31 1,2 y = 9,69E-01e -1,65E-04x 1,2 1 1 y = 1,06E+00e -1,54E-04x 0,8 0,8 [YbNH2] 0,6 [YbNH1] 0,6 0,4 0,4 0,2 0, time [s] time [s] Fig. S33. The plots of the concentrations of the NH signals (based on the 1 H NMR signal intensity) vs. time for the two different amine protons of the (P)-[YbL RRRRRR ](NO 3 ) 3 6H 2 O complex (298K, CD 3 OD). 1,2 y = 8,67E-01e -1,15E-04x 1 0,8 [PrNH1] 0,6 0,4 0, time [s] Fig. S34. The plot of the concentration of the NH signal (based on the 1 H NMR signal intensity) vs. time for the amine proton of the (M)-[PrL RRRRRR ](NO 3 ) 3 H 2 O complex (298K, CD 3 OD). S31

32 Supporting Table S1 Crystal data and structure refinement details for the (M)-[PrL RRRRRR ](NO 3 ) 3 3CH 3 CN 3 2 / 3 H 2 O, (P)-[CeL SSSSSS ](NO 3 ) 3 4CH 3 CN 3H 2 O and (P)-[LuL RRRRRR ](NO 3 ) / 8 CH 3 CN 3 3 / 4 H 2 O complexes. Empirical formula C 45 H N 15 O Pr C 47 H 75 CeN 16 O 12 C H LuN O Formula weight Temperature 100(2) K 100(2) K 100(2) K Wavelength Å Å Å Crystal system orthorhombic orthorhombic trigonal Space group P P P322 1 Unit cell dimensions a = (8) Å a = (3) Å a = (4) Å b = (8) Å b = (3) Å c = 38.92(2) Å c = (17) Å c = (6) Å Volume 5629(6) Å (2) Å (5) Å 3 Z Density (calculated) g/cm g/cm g/cm 3 Absorption coefficient mm mm mm -1 F(000) Crystal size mm mm mm ϑ range for data collection 3.1 to 36.7 o 2.60 to o 3.0 to 28.6 o Index ranges -22 h 17, -17 h 18, -19 h 19, -13 k 19, -19 k 19, -19 k 20, -38 l l l 33 Reflections collected Independent reflections (Rint = ) (Rint = ) (Rint = ) Absorption correction analytical analytical analytical Max. and min. transmission and and and Refinement method full-matrix least-squares on F2 full-matrix least-squares on F2 full-matrix least-squares on F2 Data/restraints/parameters 14547/0/ /6/ /6/629 Goodness-of-fit on F Final R indices [I>2σ(I)] R(F) = R(F) = R(F) = R w (F 2 ) = R w (F 2 ) = R w (F 2 ) = R indices (all data) R(F) = , R(F) = R(F) = R w (F 2 ) = R w (F 2 ) = R w (F 2 ) = Absolute structure parameter 0.027(15) 0.012(14) (7) Largest diff. peak and hole and e.å and e.å and e.å -3 S32

33 Supporting Table S2. Selected bond lengths (Å) for [PrL RRRRRR ](NO 3 ) 3 3CH 3 CN 3 2 / 3 H 2 O, (P)- [CeL SSSSSS ](NO 3 ) 3 4CH 3 CN 3H 2 O and [LuL RRRRRR ](NO 3 ) / 8 CH 3 CN 3 3 / 4 H 2 O crystals. Empirical formula C 45 H N 15 O Pr C 47 H 75 CeN 16 O 12 C H LuN O Ln-N (6) 2.620(4) 2.493(4) Ln-N (5) 2.708(4) 2.559(4) Ln-N (5) 2.663(4) 2.534(4) Ln-N (4) 2.645(4) 2.451(4) Ln-N (5) 2.714(4) 2.532(4) Ln-N (6) 2.697(4) 2.525(4) Ln-N (5) 2.649(4) 2.447(4) Ln-N (5) 2.657(4) 2.526(4) Ln-N (5) 2.723(4) 2.577(4) Supporting Table S3. Final distribution of species obtained after heating the solutions of the (M)- [LnL RRRRRR ] 3+ complexes in D 2 O at 318K. Ln Total time of heating [hrs] %(M)-[LnL RRRRRR ] 3+ %(P)-[LnL RRRRRR ] 3+ %L RRRRRR Ce Pr Eu Tb Er a Yb Lu a could not be determined due to signal broadening S33